Reactive disazo triazine dyestuffs made from a diamino diphenylure disulphonic acid

ABSTRACT

REACTIVE DYESTUFFS REPRESENTED BY THE FORMULA:   2-(D-N(-R)-),4-CL,6-((-((-((2-(D-N(-R)-),4-CL-S-TRIAZIN-6-   YL)-NH-),(HO3S-),X-PHENYL)-NH-CO-NH-),(HO3S-),X-PHENYL)-   NH-)-S-TRIAZINE   WHEREIN R REPRESENTS A HYDROGEN ATOM OR AN ALKYL GROUP, X IS H, CH3 OR CL AND   D-N(-R)-   REPRESENTS THE RADICAL OF A WATER-SOLUBLE COLOURED COMPOUND. THESE DYESTUFFS ARE USEFUL AS REACTIVE DYES FOR COLOURING CELLULOSIC TEXTILES AND GIVE AN UNUSUALLY HIGH DEGREE OF FIXATION DURING DYEING AND PRINTING PROCESSES. THE DYESTUFF ARE FURTHER CHARACTERIZED BY THEIR OUTSTANDING LIGHT FASTNESS.

3,658,782 Patented Apr. 25, 1972 3,658,782 REACTIVE DISAZO TRIAZINE DYESTUFFS MADE FROM A DIAMINO DIPHENYLUREA DISUL- PHONIC ACID l, Geoffrey Grifiiths and Cecil Vivian Stead, Manchester,

England, assignors to Imperial Chemical Industries Limited, London, England No Drawing. Filed Mar. 3, 1969, Ser. No. 803,977 Claims priority, application Great Britain, Mar. 8, 1968,

Int. Cl. coin 33/12, 62/08 US. (:1. 260-453 4 Claims ABSTRACT OFTHE DISCLOSURE Reactive dyestuffs represented by the formula:

m! 80 8 I D-N- lili-CO-llll I -7-.D

t t a In X 80 X wherein R represents a hydrogen atom or an alkyl group, X is H, OH, or Cl and represents the radical of a water-soluble coloured .compound. These dyestuffs are useful as reactive dyes for colouring cellulosic textiles and give an unusually high degree of fixation during dyeing and printing processes. The dyestufis are further characterized by their outstanding light fastness.

This invention relates to new reactive dyestuffs of the triazine series, useful for the colouration of cellulose textile materials. 7 1

The manufacture of mauve dyestuffs by condensing azo dyestuflzs with cyanuric halides and then condensing two moles of the resulting dichloro-s-triazine derivative with a variety of diamines is described, for example, in the provisional specification of UK. ;Pat. No. 854,432.

United States Patent Oflice other and that the sulphonic acid groups should be in ortho position to the -'NHCONH- group.

.Thus a preferred class of dyestuffs is that in which the linking group is a 4,4-divalent-diphenylurea- 2,2 disulphonic acid radical and D-NR is the radical of a phenylazopyrazlolone compound containing a NHR group and a plurality of water-solubilising groups e.g. DNR represents a radical of the formula: I

in which R represents a methyl group or a carboxylic acid or carboxylic acid amide group,

R represents a benzene or naphthalene radical which may be substituted e.g. by C1, CH OCH NHCOCH CO H and in particular SO H.

. Such dyestuffs are distinguished by their value for use in dyeing by exhaustion methods, in which they offer a degree of fixation over a wide range of liquir-to-goods ratio not possessed by commercially-available reactive dyestufis. At the same time, the new dyestuffs provide The present invention is based on the observation that valuable cellulose-reactive dyestutfs can beobtained in an analogous manner by using a N,N"-diphenylurea disulphonic acid as the linking diamine; I j i V According to the invention there are provided'new' reactive dyestuffs represented by the general formula:

soar

Hots

. n-N o 0 l m a I a I 01 0 wherein R represents a hydrogen atom or X is H, CH or Cl and represents the radical of a water-soluble coloured compound containing a NHR group;

In the above formula, the radical D can, for example,

an alkyl group,

shades oft-very good light fastness, whereas previously known dyestuffs of similar structure are usually deficient in this property.

The invention also provides a process for manufacture of the new reactive dyestuffs which comprises reacting cyanuric chloride, in either order, with one molecular proportion of a water-soluble dyestutf. of the formula:

' D-NHR (4) and with one-half molecular proportion of a diamino diphenyl-urea disulphonic acid which may contain CH or Cl as a substituent in each benzene ring. 7

The above process can conveniently be carried out by stirring a suspension of the cyanuric chloride in an aqueous medium with the dyestufi of Formula 4 at a temperature of O-to 20 C. until one chlorine atom of the cyanuric chloride has been replaced by the radical of the dyestutf, then adding the diamine and continuing reaction at a slightly higher temperature, usually in the range 30 to 50 C. until a second halogen atom on the triazine represent the radical of a water-soluble coloured com- 7' pound of the azo, anthraquinone or phthalocyanine series, e.g. a monoor bis-azo dyestulf which may or may not be metallised.

The amino groups in the depicted 'benzene rings may nucleus has reacted with each amino group. Alternatively, the cyanuric chloride can be reacted first with the diamine at the lower temperature to form a bis(dichlorotriazine) derivative and then with the dyestuif at the higher temperature. The condensations are preferably carried out at a pH otfrom 4 to 7, adding in acid-binding agent to neutralise the hydrochloric acid as it is liberated during the reaction. When reaction is complete the new reactive dyestuffs can be isolated by the usual techniques adapted for isolation of water-soluble reactive dyestufis, for example, by salting out and filtration, or by spraydrying the reaction mixture in which the dyestufi has been formed. If desired, stabilisers, for example alkali metal hydrogen phosphates, can be added.

' As 'examples of 'diaminodiphenylurea 'disulphonioacids IGH-V-NHR wherein the anthraquinone nucleus may contain an additional sulphonic acid group in the 5-, 6-, 7- or 8-position and V represents a bridging group which is preferably a wherein D represents a radical of the types defined for D in classes (ii) and (iii) above and K represents the radical of an enolisable .ketomethylene compound such asan'acetoacetarylide or a 5-pyrazolone having the -OH group in tat-position to the azo. group.

(vii) 1: l -metal complex, especially the copper complex,

, compounds'of those dyes of Formulae 6', 8 and 9 (wheredivalent radical of the benzene series, for example phenylene, diphenylene or 4,4-'divalent stilbene or azobenzene radicals. It is preferred thatV should contain one sulphonic acid group for each'benzene ring present. R has the meaning stated above. 5

(ii) Monoazo compounds of the formula:

$01K 5 6 NHR wherein D represents a mono or di-cyclic "aryl radical which is free from azo groups and NHR groups, the

-NHR group is preferably attached to the 6-,7- or 8-position of the naphthalene nucleus, and which may .con-

tain a sulphonic acid group in the 5- or 6-positionxof the nanthalene nucleus.

D may represent a radical of the naphthalene or bone zene series which is free from azo substituents, for example a stilbene, diphenyl, benzthiazolyl/phenyl or-diphenylamine radical. Also in this class are 'to be considered the related dyestufis in which the NHR group, instead-'of'being attached to the naphthalene nucleus, is attached to a .ben-. zoylamino or anilino group which is attachedto the 6-, 7- or 8-position of the naphthalene nucleus.

' Particularly valuable dyestutfs are obtained from those Y wherein D represents a sulphonated phenyl or naphthyl radical, especially those which contain a -SO H group in ortho position to the 2120 link; the phenyl radical may in D K; and ,K: have all the respective-means stated) which contain a metallisablef (for example, a hydroxy, loweryalkoxy -or'carboxylieacid) 'group"ortho-.to the am group in D fly i 1 (viii) Phthalocyanirie compoupds'of the formula:

sog-tn.

. 7 Po Q (S0iNH VlNHR) 10) wherein Pc represents the phthalocyanine nucleus preferably of copper phthalocyanine, :0 represents a hydroxy and/or a substituted or unsubstituted amino group, V1 represents a'bridging group, preferably an aliphatic, cycloaliphatic or aromatic bridging group, n represents l, 2

' (ix) Nitro dyestutfsof'the formula:

BX-NHB:NHR

N0: '(11 wherein B and B; represent monocyclic aryl nuclei,the nitro group in B, being ortho tothe NH group. i As examples of compounds of classes (i) to (ix) there may he mentioned the following:

be further substituted'for example, by halogen atoms'such j wherein D stands for a radical as defined for class (ii) or class (iii) and D is a 1:4-phenylene'or a sulpho-l l-naphthylene or a stilbene radical; the benzene nuclei in Di'and D may contain further substituents such as halogen atoms, or alkyl, alkoxy, carboxylic acid and acylaminogroupsl:

(v) Monoor dis-azo compounds of the formuda':

wherein D repres ents an arylene radical such as a radical of the azobenzene, azonaphthalene or phenylazonaphthaa 1-amino-4-t 3' -amino- 2f 4'; 6'-trimethylanilino) In Class (D I Lamina-4'-(4'-methylaminoanilino) anthraquinone-2:3-

' disulphonic acid,

anthraQuinone-ZJi-disulphonic acid,

I I V In Class(ii)v G-amino-khydroxy-Q-(2-sulphophenylazo')naphthalene- 3-sulphonic acid, J 1

8-amino-1-hydroxy-2-(2'-sulphophenylazo)naphthalene 3:6-disulphonic acid, I

7-amino-2-(2' 5"-disulplio'phenylazo) l-hydroxynaphthalene-3-sulphonic acid,

I 7-methylamino-2- 2'-sulphophenylazo) l-hydroxynaphthalene-B-sulphonic acid, 7-methylamino-2-(4-methoxyZ-sulphophenylazo)-1- hydroxynaphthalene-3-sulphonic acid,

8-(3'-aminobenzoylamino)-1-hydroxy-2-(2'-sulphophenyl- "azo)naphthalene-.3:6disulphonic acid,

8-amino-1-hydroxy-2:2-azonaphthalene- 1' 3 5'-6- tetrasulphonicacidg 61-ramino-l-hydroxy-Zd4'-acetylamino-2'-sulphophenyl- ,azo)naphthalene-3-sulphonic acid, 6 -,methylarnino-l-hydroxy-Z-(4 -methoxy-2'-sulphophenyl azo)naphthalene-S-sulphonic acid, 1

S-amino-l-hydroxy-2 phenylazonaphthalene-3':6-

'dis'ulphonic acid, A r 8-amino-1-hydroxy-2 2'-azonaphthalene--1 3 6-trisul-- phonicacid, 7 fi-amino-l-hy'droxy-Zl4f methoxy-2f-su1ph0phenylazo) naphthalene-3-sulphonic acid,

Alternatively, the .cyanuric chloride can be condensed with one-half mole of the. diaminodiphenylurea. disulphonic acid and then with one molecular proportion of an aromatic compound which contains an acylatable amino group and which after condensation is still capable of coupling with a diazonium compound, and coupling the resultant product with two moles of a diazotised aromatic amine.

Examples of suitable aromatic compounds useful for condensation in this connection include aminophenols, aminonaphthols and aromatic diamines.

The invention also provides a process for manufacture of the new dyestuffs in which the NR group is a substituent on a group of the formula:

. present in D, R representing H, alkyl or hydroxyalkyl and V an alkylene, cycloalkylene, aryl or alkaryl radical which'maybe substituted, which comprises reacting a coloured compound having. .asulphonic acid chloride group and preferably 1 or more sulphonic acid. groups with one-halflof' one molecular proportion of a'diamine of the formulas wherein R, R V and X have the meanings stated above.

1 This process can conveniently be carried out by stirring the reactants in an aqueous medium in the presence of an acid-binding agent, which, to avoidhydrolysis-of the chlorine atoms on the triazine nuclei of the (ii-amine,- is preferably added at a rate which maintains the mixture at a pH of from 6 to 8. Suitable acid binding agents for this purpose include, for example, sodium hydroxide, carbonate and bicarbonate or the corresponding potassium compounds.

Asexamples of coloured compounds which maybe used, there may be mentioned the chlorosulphonation products of copper phthaloeyanine or 1,4-diarylaminoanthr'aquinones or the products obtained by treating azo, anthraquinone or copper phthalocyanine compounds containing sulphonic acid groups with reactants capable of convertingSOgI-l to SO CI erg. chloros'ulphonic acid, thionyl chloride, phosphorus pentachloride and phosphorus trichloride.

Compounds of Formula 14 can be obtained by reacting together a diamine of the formula:

n nnv unn 15 wherein R, R and V have the meanings stated above with a'bis(dichlorotriazine) derivative of a'diamino diphenylurea disulphonic acid which may contain CH or Cl as a ,substituent in each benzene ring. l

As examples of-diarm'nes of Formula lithere may be mentioned ethylene and hexamethylenediamines, N-fl-hydroxy-ethyl-ethylene diamine, diethylene triamine, 1,4-diamino cyclohexane, mand p-amino-benzylamines and mand p-phenylene diamines and their monoand di-sulphonic acids.

The new reactive dyestuffs are valuable for colouring cellulose textilematerials comprising natural or. regenerated cotton. For colouring such materials, the new dyestuffs are preferably applied, either by a printing but preferably a dyeing process, to the cellulose textile materialszin conjunction with a treatment with an acid binding agent, e.g. caustic soda, sodium carbonate, phosphate, silicate or bicarbonate, which may be applied to the cellulosetextile material before, during or after the application of the dyestutf. When so applied the new g, vention which may be obtained when the 11.4 parts of the dyestuffs react with the cellulose and yield shades possessing excellent fastness to washing. 'j

The invention may be illustrated but is not. limited by the following example in which the partsare by weight:

. EXAMPLE .t

A solution of 3.7 parts of cyanuric chloride in30 parts of acetone is'run into an ice-cold solution of 11.4 parts of the trisodium salt of 1-(4'-sulphophenyl) -3-carboxy-4- (2"-sulpho-5"-aminophenylazo)-5-pyrazolone in 200'parts of water. 20 parts of a N solution of sodium'hydroxide are subsequently added to neutralise generated acidity. A solution of 4.5 parts of the disodium salt of 4,4'-diaminodiphenylurea-2,2-disulphonicacid in" 100 parts of water is added and the mixture is heated for -l /z hours at 35 C. whilst 20 parts of N sodium hydroxide solution are added to keep the solution neutral. 100 parts of potassium chloride are then added and the precipitate is filtered off and dried at 50C.

The dyestufi so obtained isz-a'yellow powder; on analysis it is found to contain 2.08 atoms of organically bound chlorine per molecule'When'applied to cellulosic textile materials in the, presence of acid-bindingagents it yields greenish-yellowshades of excellent fast'ness to light and wet treatments. p I The fixationof the above dyestuif was measured .on cotton, and viscose rayon materials by dyeing at 5:1 and 20:1 liquor-to-goods ratios at'80 C. as follows;

An amountof dyestutf correspondingto 14 mole was dissolved in water and made up to the appropriate volume for a 5:1 or 20 :1 dyeing. Common salt at the rate of 60 g./l. was added and the solution washeated to C. The materials (a 5 g. hank in the case of 212011 dyeing of cotton, piece material in'the other three cases) was added Liquor to goods rat-lo Material a 6:1 7 20:1

Cotton, percent 76 75 Viscose rayon, percent.. 87

Similar dyeingsusingtan amount of dye corresponding to ,4 mole and salt at the rate-of gL/l. gave the'folq lowing results: I

- Liquor to goods ratio Material 5:1 2];

Cotton, percent 70 72 Viscose rayon, percent.-. 81

Not only does this dyestulr' give unusually high fixations by dyeing, but also by printing. For example fixations of 85% or greater are obtained-from print pastes containing sodium carbonate, the, resultant prints havingexcellent freedom from staining during washing treatments.

Table 1 gives further'examples of dyestulfs of the intrisodium salt of l-(4' sulphopheny1)-3-carboxy 4-(2"- sulpho-j' -aminophenylazo)sfi pyrazolone used in Examobtained when the dyestuft' isapplied to cellulose textile materials in the presence of an acid binding agent.

. TABLE I I II v III Example 2. Trisodium salt oi 2 4'-amino-2'-ureidophenyl)napthalene-3,6,8-trisulphonic acid Yellow. Example 3- Trisodlum salt oi 6-(l,5-disulphonaphth-2-ylazo)-methylamino'E-naphthol-7-sulphonic acid- Reddish-orange. Example 4. Disodium salt of 1-(2,5-dichloro-4'sulphophenyl) -4-(5"-amino-2'-sulphophenylazo)-3-methyl-5-pyrazolone- Greenish-yellow. Example 5. Disodium salt oi 7-phenylazo-l-amino-s-naphthol-3,6-disulphonic acid Blue-red. Example 6 'Irisodium salt oi 7-(2'-sulphophenylazo)-1 amino-8-naphthol-3,6-disulphonic acid 'Do. Example Trisodium salt 4-[4'(2.5-disulphophenylazo)-25-dlmethylphenylazo]-1-maphthylanune-8-sulphonic acid. Orange. Example Tigsodiunlslalt oiidthe copper complex oi 7-(2-hydroxy-3-chloro-5-sulphophenylazo)-1-amino-8-naphthol3,6- Purple.

su p o 0 ac Example 9-.. Tzggghilmnsalt (iii the copper complex oi 6-(2-hydroxy-3',5'-disulphophenylazo)-2-methylamino -naphthol- Rubine.

p o c ac Example 10 Tagaaodiug salltdoi the copper complex oi 6-(2'-hydroxy-3,6'-disulphophenylazo)-2-amino-5-naphthol-1,7- Do.

. p o c ac Example 11 Dlsodium salt oi 1-amino-4-(4-aminoanilino)anthraquinone-2,3'-disulphonic acid Greenish-blue. Example 12.- Disodium salt 0i 1-amino-4-(4-methylaminoanillno) enthraquinone-2,3'-disulphonic acid--. Blue. Example 13.. Disodium salt of l-amino-4-(3'-aminoanilino)anthraquinone-2 4-disulphonic acid Do. Example 14.. Disodium salt oi l-amino-4-(3-amino-2,4,6'-trlmethylanilinos anthraquinone-2,5-dlsu1phonic acid.- Reddish-blue. Example 15.. Dlsodlum salt oi 6-amino-l-hydroxy-2-(2-sulphophenylazo)naphthalene-B-sulphonic acid Orange. Example 16.. Trisodium salt oi 6-amino-1-hydroxy-2 (2,5-disulphophenylazo)naphthaylene-Zl-sulphonic acid-.. Do. Example 17.. Disodium salt oi 6-methylamino-1-hydroxy-2-(2-sulphophenylazo)naphthalene-3 sulphonle acid.. Do. Example 18.. Disodium salt oi 7-methylemino-2(4-methoxy-2-sulphophenylazo)-1-naphthol-3-sulphonic acid.-.. Red. Example 19-. Trisodium salt oi 8-(3aminobenzoylamino)-2-(2sulphophenylazo)-1-naphthol-3,6-dlsulphonic acid.. Blue-red. Example 2 0.. 'letrasodium slt oi 8-amlno-1-hydroxy-2,2'-azonaphthalene-l',3,5,6-tetrasulphonic acid Do. Example 21-- Trisodium salt oi S-amino-1-hydroxy-2,2-azonaphthalene-l,8,6-trlsulphonlc acid Do. Example 22-. Disodium salt of 6-amlno-2-(t'methoxy-2-sulphophenylzao)-1-naphth0l 3-sulphonic acid Scarlet. Example 2 3.. Disodium salt oi 6-methylamino-2-(4-methoxy-2-sulphophenylazo) -1-naphthol-3-sulphonic acid. Do. Example 24.- Trisodinm salt of 6-arnino-l-hydroxy-2,2-azonaphthalene-1,3,6-trisulphonlc acid Reddish-orange. Example 25-. Trisodlum salt of 7-amino-1-hydroxy-2,2-azonaphthalene-l',3,5-trisulphonic acid Red. Example 26-- Tetrwodlum salt oi G-amino-l-hydroxy-Z,2-azonaphthalene-1,3,5,5-tetrasulphonic acid Reddish-orange.

... isaalt oi 8-amino-2-[4-(2"-sulphophenylazo)-2-methoxy-5-methylphenylazo]-1-naphthol-3,6-disul. Navy-Blue.

p o cac Example 28 Disodium salt oi 2-(4'-amlno-2-methylphenylaso)riaphthalene-4,8-disulphonic acid Yellow.

. Disodium salt oi 2(4-amlno-2-acetylaminophenylazo) naphthalene-5,7-disulphonlc acid- Yellow Disodium salt oi 4-nitro-4-(4(-methylaminophenylazo) stilbene-2,2-d.isulphonic acid Yellow.

Tetrasodium salt of 4-[4-(2,5",7"-trisulphonaphtl1-1-ylazo)-2,5-dirnethylphenylaaol l-naphthylanifne Yellow-Brown.

-6-sulphonic acid.

Trisodium salt oi 4-[4'-(4"-sulphophenylazo)-2-sulphophenylazo]-1-naphthylamine-6-sulphonic acid Orange- Brown: Example 33 'Irisodium salt oi 1-(4'-sulphophenyl)-3-carboxy-4-(4-amlno-3"-sulphophenylazo)-5-pyrazolone.'. Yellow. Example 34 Trisodium salt oi 8-acetylamino-2-(3-amino-4-sulphophenylazo-1-naphthol-3,6-disulphonic acid Red. Example 35 Trisodium salt oi 8-pl1enylamino-2-(4-amino-2-sulphophenylazo) 1-naphthol-3,6-dilulphonic ac Blue. Example 36 Disodium salt oi 6-ureido-2(5-amino-2-sulphophenylazo)-1-napthtol-3-sulphonic acid Orange Example 37 Trisodium salt 0! 8-benzoylamino-2(5-amino-2-sulphophenylazo)-1-naphthol-3,6-disulphonic a Blue-Red Example 38.- Trlsodium salt oi 1-(4,8'-disulphonaphth-2f-yl)-3-methyl-4-(5t-amino-2"-sulphophenylazo)-5-pyrazo Yellow Example 39-- 'lrisodium salt of 1 '-methyl-3-amino-5-sulphophenyl)-3-carboxy-4-[2"-sulphophenylazo1-5-pyrazolone-. Do. Example40 Trislodi um 1salt oi the copper complex oi 6-amino-2-(2-hydroxy-fi'sulphophenylazo)-1-naphthol-3,6-disul- Rubine.

i po cac v Example 41 Trisodium salt oi the copper complex oi 6-methylamino-2-[4'-(2",5"-disulphophenylazo 2-methoxy-5'-methyl- Navy-blue.

. v phenylazol-l-naphthol-a-sulphonic acid. 7 Example 42 Trisodium salt oi the copper complex 01' 8-amino-1;2-dihydroxy-l,2-azonaphthalene-3,4,6-trisulphonic acid.. Blue. Example 43..- Tetriaisodium salt oi the copper complex oi 8Famimo-1,l dlhydroxy-2,2-azonaphthalone-2,4,6,8'-tetrasulphonic Do. Example 44 Isialt oi dthe copper complex oi 8-amino-2-(2-hydroxy-3-sulpho5-aminophenylazo)-1-naphthol-5,7- Do. p 0 caci H l Example 45 Trisodium salt oi the'copper complex oi 8-amino-2-(2'-hydroxy-4-sulpho-6'-amlnonaphth-1-ylazo)-1-naph- Do.

thol-5,7-disulphonic acid. E Example 46 Triso'dium salt oi the copper complex of 6-(4'-amlno-3-su.lphophenylamlno)-2-(2"-hydroxy-3"-nitro-5"- Purple.

sulpho'phenylazo)-1-naphthol-3-sulphonic acid. I Example 47 Disodium salt oi 4-amlno-2'-nitrodlphenylamine-3,4'-disulphonic acid Yellow. Example 48-- Pcatfioiliiulm sell? 01 8-amino-7-(2 ,5-disulphophenylazo)-2- "-amino-2"-sulphophenylazo)-1-naphtnol-3,6- Navy-blue.

s p o c ac l Example 49 Trisodiumsalt of 2-amino-1-(4'-amino-2,5disul hophenylazo) -8-na phthol-6-sulphonic acid Red. Example 50.. Tetrasodium salt of 3-(3-amino-4'-sulphophenylsulphaznyl copper phthalocyanine-trisulphonic acid. Turquoise.

Y EXAMPLE s1- w. EXAMPLE s4 '-='A'*solution of 3.7 parts of-cyanuric chloride in 30"par.ts A solution of 3.7 parts of cyanuric chloride in 30 parts of acetone is run into an ice cold solution of 4.5 parts of of acetone is run into an ice cold solution of 11.4 parts the disodium salt of 4,4'-diaminodiphenylurea-3,3'-disulof the trisodium salt of 1-(4-sulphophenyl)-3-carboxy1-4- phonicacid in 100 parts of water. 20 parts of a N solu- .5 "-sulpho-5"-aminophenylazo)-5-pyrazolone in 200 parts tion of sodium hydroxideiare subsequently added to neuof water. 20 parts of a N solution of sodium hydroxide are tralize generated acidity. A solution of 9.3'parts of the 'disubsequently added to neutralize generated acidity. A sodium salt 'of 2-(4-amino-2'-methylphenylazo)naphthasolution of 4.7-5 parts of the disodium salt of 2,2'-dimethyllene-4,8-disulphonic acid in 200 parts of water is added. 3,3-diaminodiphenylurea-5,5'-disulphonic acid in 100 and the mixture stirred and heated for 20 hours at 35 C. parts of water is added and the mixture is heated for 3 /2 whilst 20 parts of a N solution of sodium hydroxide are hours at 35 C. whilst 20 parts of a N solution of sodium added to 'keep the solution neutral."100 parts of potassium hydroxide are added to keep the solution neutral. 500 parts chloride are then added and Y the precipitate isfiltered of potassium chloride are then added and the precipitated oil and dried at 50 C. dycstuif filtered oil and dried at 50 C.

The dyestuii so obtained is afyellow powder which 60. The dyestuff so obtained is a yellow powder which, when applied to cellulosic textile materials in the presence when applied to cellulosic textile materials in the presence of acid binding agents yields yellow shades of excellent of acid binding agents, yields greenish-yellow shades of fastness to light and 'wet treatments. excellent fastness to light and wet treatments.

Table 2 gives further examples ofsimilar yellow dyestuifs of the invention which may be obtained when the E LE 5 parts of 4,4'.-d i mi odi henylurea-3,3'-disulphonic A solution of 3.7 parts of cyanuric chloride in 30 parts acid used in Example 51 is replaced by the equivalent of acetone is run into an acid cold solution of 4.5 parts amount of the compound listed in Column II of Table 2. of the disodium salt of m p y TABLE, 2 I r sulphonic acid in 100 parts of water. 20 parts of a N solution of sodium hydroxide are subsequently added to neu- I II. I tralize generated acidity. A solution of 4.2 parts of the Example 52 3,-3-diaminodiphenylurea 4,4-disulphonic monosodium salt of 1,3-phenylene diamine-4-sulphonic acid. acid in parts of water is added and the mixture stirred Example 53 .3,-3'-d-iaminodiphnylurea-6,=6-disulphonic and heated for 20 hours at 35 C. whilst 20 parts of a acid. 5 N solution of sodium hydroxide are added to neutralize 1-1- 12 ge erated.aeiditnIheselutienisthen eqo edttqrflfrC-taed; sthereinmnsi sdi-azqrrtrieulphqnapbthylsreadmParis,list; 25 parts of a 2 N solution of hydrochloric acid added follo'ii dby '10, parts-era '2 'N "soru'treh or fs'odiumfnitrite. f After 30 minutes I eiicess nitrous acid is destroyed by the v- ..1 v additibnot su'lphamic acid and a solution of 6.75 pauses '5 v the disodium salt o f l-( V-suhahophenyl)-3-carboxy-5-v pyrazolone in 100 parts of water is added; Suflicient bi so "1'" h I dium hydroxide is added to raise to pH to 7 and after 1 p v v hour 100'parts of potassium chloride are added'andthe precipitateddye is filtered 0E and dried at"50-= C. 1-0-' he. yellow p w r, 9 ob n s n l nv P m-t.

ties to the dyestuff described in Example 1 EXAMPLE.- 56 1 I [17 A solution of 3.7 parts of cyanuric chloride 'in ,30'-lpa'rts to of acetone is run into an ice cold solution'of 4.5 parts of the disodium saltof 4,4-diaminodiphenylurea-2;2'-di"- sulphonic acid in 100 parts of water. 20 p'artsof'af ;N; some 1 '7 tionpf sodiumhydroxide' are subsequently added. "tneu tralize generated acidity. A solution of 5.2partsp the I p morfosodiimi salt of2 amino 5naphthol-7sulphonic acid 7"" 2-, g I .v in 100 parts ofrwater is added and the mixture stirred for m WhlCh R represents CH or CONH 4 hours at 35 Crwhilst12OLpa'rt's ofa-Nsolution' of rrepresentstabenzene"or naphtha -ncle1r 'ts1whiht1s sodium hydroxide are added to neutralize generatedfacid 5 Substituted or,substituted by: fro1nj""1 t ;3 substitttentsgsei ity. The solution is cooled to 0 C." and a solution of the Iected from Cl, CH OCH NI-IC CH ',"CO"H'a'nd diazoniurn salt derived from 5.9 parts of the-disp'dium salt ,f SO H; If f: i v i 1' of aniline-2,5-disulphonic acid in IOU-liartsfot! Water '5 then addedfollowed-by sufficient N sodiurrrjhydroxide o i 1; a raise the pH to 7..Ihe solution is stirred for 11 liour and" 1 t 100 parts of potassium chloride added. Thepprecipitated 2 orange dyestulf is filtered OE and dried at 50 (3. When applied to cellulosic textile materials in the presence of an V acid binding agent it yields orange shades of excell" t fastness to light and wet treatments. L L

We claim: I v

1. A reactive dyestuff represented by the forinular" .SQ-A dyestuff as claimed, in claim-1 represents aradical of the formula;

wherein R represents hydrogen or lower alkyl, CH orCland 7 c 1r represents the radical of a water-soluble nnmetalliied monoazo or lgl copper complexmonoazo cornpound having the NR group attached to a carbon atom thereof, DNR being selected from the group consisting of:

( i k 1 Dl-t=N-. t v NR n r, or a radical of the formula 'SOgH- I I; r V I 7 5; v 50: V w wherein D is phenyl, 2-sulphophenyl, 4smethoxy-2-tsul- -..1-'-NR .v phophenyl, 2,5-disulphophenyl, l-sulphonaPhth-Z-yl; and N 1,5-disulphonaphth-2-yl; I

3 in which R represents CH CO H or CONI-I and R, lected from C1, CH OCH NHCOCH CO H and represents a benzene or naphthalene nucleus which is un- SO H. substituted or substituted by from 1 to 3 substituents se- 4. The dyestutf of the formula:

References Cited UNITED STATES PATENTS FLOYD D. HIGEL, Primary Examiner US. Cl. X.R. 

